CN108853866B - 一种甲醛清除剂及其应用 - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
本发明提供一种甲醛清除剂，特别涉及一种以EGCG棕榈酸单酯为活性物质的甲醛清除剂。本发明公开的甲醛清除剂，其组分按重量百分比包括：EGCG棕榈酸单酯2‑4%，聚乙二醇600单油酸酯1‑3%，1,3‑丙二醇2‑5%，磷酸二氢钠0.5‑2%。本发明公开的EGCG棕榈酸单酯型甲醛清除剂基于改性天然产物活性分子，绿色环保，除醛效果稳定持久，适用于板材及家具中甲醛的清除。
Description
技术领域
本发明涉及除甲醛领域，特别涉及一种以EGCG棕榈酸单酯为活性物质的甲醛清除剂。
背景技术
甲醛是一种具有刺激性和窒息性的无色、易挥发的有毒气体，对人体健康的影响主要表现在嗅觉异常、刺激、 过敏、肺功能异常、肝功能异常和免疫功能异常等方面。世界卫生组织已将甲醛确定为致癌和致畸性的***反应源，国际癌症机构（IARC）将其列为第一类致癌物质，我国也已将其列为有毒化学品优先控制名单。
目前，以甲醛为聚合单体生产的脲醛树脂、酚醛树脂、三聚氰胺树脂等因其成本低、粘黏强度好、适用范围广等特点而被大量应用于密度纤维板、刨花板、胶合板、免漆板、墙布胶黏剂、皮革胶黏剂等室内装饰性材料的生产制程中。而上述以甲醛为聚合单体生产的树脂胶黏剂中含有的大量游离甲醛会在涂料固化、材料成型等后续过程中释放出来。调查统计表明，80%新装修家庭室内空气质量达不到国家标准，而这其中又有90%是由于甲醛超标引起的。因此，甲醛已成为室内环境的主要污染源。
随着人们对健康居住环境和室内空气质量的愈发重视，众多的专利及文献报道了甲醛消除方法。其中，甲醛清除剂一般是指在特定条件下可以与甲醛发生化学反应，使其生成稳定化合物的功能性组合物。常见的甲醛清除剂其技术原理包括氧化型和亲核试剂型等，其中氧化型中常用的强氧化剂有二氧化钛、钛酸酯、过氧化氢、次氯酸、二氧化锰、过硫酸氢钠、过硼酸钠等可促进甲醛发生氧化反应的物质；亲核试剂型是指能与甲醛发生亲核加成反应的氨类物质如尿素、氨基尿等，胺类衍生物如肼、苯肼、羟氨等，酚类物质如含有间苯二酚结构的酚类物质等，次甲基活泼氢（α-H）的化合物如乙酰乙酸甲酯、丙二酸二甲酯等。
相关专利，如中国专利申请号201310567823.8公开了一种用于消除甲醛的纳米级二氧化钛溶胶的制备方法，其组分按重量为钛酸丁酯20-60，去离子水600-1000，冰醋酸40-80，浓盐酸1-3，无水乙醇40-80。中国专利申请号200410096091.X公开了一种低游离甲醛释放量人造板用触媒，该触媒由氧化物、含 有NH4基或NH2基的化合物、强酸弱碱盐、氧化剂等物质组成；中国专利申请号 201610622956.4公开了一种除甲醛空气净化剂，其原料按重量份剂包括茶叶提取物5-10份、纳米抗菌剂4-8份、硫酸钠、过氧化氢及氯化钠5-10份、流平剂0.2-0.5份、稀土激活剂0.2-0.5份、植物香薰精油0.5-2份、茶多酚1-3份、消泡剂1-2.5份、去离子水200份等。
在已公开的消除甲醛的技术方案中，强氧化剂及酸性甲醛清除剂使用过程中可能会对五金件及油漆表面产生腐蚀；核试剂型甲醛清除剂大多数含有无机铵或有机胺或肼类等物质，该类物质在一定条件下释放出有毒气体氨气等，从而造成室内空气的二次污染；天然产物型甲醛清除剂，如茶叶提取物，该类物质作为一类毒副作用小的天然活性物质，因其结构中的间苯三酚砌块与甲醛具有很强的反应活性，因此将茶叶提取物直接用于清除治理甲醛的专利也多有报道，然而由于儿茶素类物质分子中独特的多酚羟基结构，使得其在光照、高温、潮湿等条件下容易发生氧化、聚合等反应，从而使其除醛活性快速失效。
发明内容
本发明提供一种甲醛清除剂，尤其是一种以EGCG(表没食子儿茶素没食子酸酯)棕榈酸单酯为除醛活性物质的甲醛清除剂。EGCG是茶叶提取物儿茶素类中活性最好的物质，它是以2-苯基苯并吡喃为基础结构的类黄酮类分子，在其分子结构中的间苯三酚砌块与甲醛具有很强的反应活性，且与苯并吡喃相连的苯环上的羟基数量基本不影响其与甲醛的反应活性。EGCG棕榈酸单酯是EGCG与棕榈酰氯进行酯化反应得到的活性物质，该分子在保留了与甲醛具有很强的反应活性的间苯三酚砌块的同时，在B环C-3 位引入了棕榈酸酯基。通过修饰天然产物得到的EGCG棕榈酸单酯，极大地提高了EGCG母核的抗氧化性、亲油成膜性能等。
在具体的实现方式上，本发明通过增溶剂1,3-丙二醇、聚乙二醇600单油酸酯及接近于中性的缓冲溶液体系，改善了EGCG棕榈酸单酯的水溶性，同时，磷酸二氢钾和磷酸氢二钠的缓冲体系提供了EGCG棕榈酸单酯最佳反应活性所需的pH值。
本发明公开的甲醛清除剂其优点在于：所述的EGCG棕榈酸单酯为基于茶叶提取物得到的衍生物，毒副性小，绿色环保；所述的EGCG棕榈酸单酯反应活性高，除甲醛效果好；所述的EGCG棕榈酸单酯抗氧化性强，以其为活性物质的甲醛清除剂稳定性好；所述的EGCG棕榈酸单酯亲油成膜性好，能在木质板材、皮革、油漆等表面形成致密的除甲醛活性膜。
具体实施方式
本发明提供了一种甲醛清除剂，其组分按重量百分比计为：
EGCG棕榈酸单酯0.5-4%；
聚乙二醇600单油酸酯1-3%；
1,3-丙二醇2-5%；
磷酸二氢钾 1-5%；
磷酸氢二钠 1-5%；
纯水 84-94.5%。
所述的EGCG棕榈酸单酯0.5-4%，最优选为1%。
所述的聚乙二醇600单油酸酯2-4%，最优选为3%。
所述的1,3-丙二醇1-3%，最优选为2%。
所述的磷酸二氢钾1-5%，最优选为3.4%。
所述的磷酸氢二钠1-5%，最优选为3.5%。
其余组分为纯水。
实施例：按照本发明的最佳配比，依次将87.1份重量比的去离子水，3份重量比的聚乙二醇600单油酸酯（ 江苏省海安石油化工厂），2份重量比的1,3-丙二醇，3.4份重量比的磷酸二氢钾，3.5份重量比的磷酸氢二钠和1份重量比的EGCG棕榈酸单酯（杭州普丽美地生物科技有限公司），搅拌至澄清溶液，即得本发明所述最优比例的甲醛清除剂。
喷涂在板材、皮革、油漆面的本甲醛清除剂用量为10-200g/m2，最佳为30-90 g/m2。
表1为参照GB/T 18204.26（公共场所空气中甲醛测定方法）及GB 185880-2001(室内装饰装修材料，人造板及其制品中甲醛释放限量)要求，平行对比测定了素板（未经本发明所述甲醛清除剂处理的板材）和测试板（经本发明所述甲醛清除剂喷涂处理过的对应对照样板）的甲醛释放量（mg/L）。其中，甲醛清除剂用喷枪均匀喷涂于对应的测试板的表面，喷涂量为50g/m2，喷涂后室温晾干，在其后的第2、10、20、30天测定其甲醛释放量。
表1 素板及测试板的甲醛释放量。
以上平行实验表明，未经除甲醛处理的10mm厚高密度板、15mm厚高密度板、10mm厚泡花板、15mm厚泡花板、15mm厚复合地板胶合板，其甲醛释放量均不同程度地超过国标规定El级板的范围，其中15mm厚高密度板甲醛释放量高达3.7 mg/L；经本发明所述甲醛清除剂处理过的对应的测试板甲醛释放量在其处理后第2、10、20、30天的测试值均小于0.05mg/L，完全符合国标规定El级板的要求。
Claims (7)
1.一种甲醛清除剂，其组分按重量百分比计为：EGCG棕榈酸单酯0.5-4％；聚乙二醇600单油酸酯1-3％；1,3-丙二醇2-5％；磷酸二氢钾1-5％；磷酸氢二钠1-5％；纯水84-94.5％。
2.根据权利要求1所述的甲醛清除剂，EGCG棕榈酸单酯的重量百分比含量为1％。
3.根据权利要求1所述的甲醛清除剂，聚乙二醇600单油酸酯重量百分比含量为3％。
4.根据权利要求1所述的甲醛清除剂，1,3-丙二醇的重量百分比含量为2％。
5.根据权利要求1所述的甲醛清除剂，磷酸二氢钾的重量百分比含量为3.4％。
6.根据权利要求1所述的甲醛清除剂，磷酸氢二钠的重量百分比含量为3.5％。
7.根据权利要求1所述的甲醛清除剂，其余组分为纯水。
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